JP6730264B2 - UV blocking to improve glass transparency - Google Patents

Description

Cross-reference of related applications

This application is incorporated by reference in its entirety herein, and is hereby incorporated by reference in its entirety into U.S. Provisional Patent Application No. 62/055,275, filed Sep. 25, 2014, 35th U.S. Code. Claims the benefit of priority under Article 119 of the Patent Act.

The present disclosure relates generally to glass articles, and in particular to glass articles used as covers or display glasses that are resistant to ultraviolet (UV) photodarkening.

Glass, such as tempered glass, is used as a cover plate or window for portable or mobile electronic communication and entertainment devices such as mobile phones, smartphones, tablets, video playback devices, information terminal (IT) devices, laptop computers and the like. Can be done. As used herein, the term "cover plate" or "cover glass" includes windows and the like in display and touch screen applications, as well as other applications requiring transparency, high strength and abrasion resistance. Be done. In addition, the cover glass can be used as a decorative piece such as a back surface and a side surface of an electronic device. In addition, other glasses that are not chemically strengthened are used as display glasses.

It has been found that exposure to ultraviolet light causes discoloration of the glass, which also affects the sharpness and resolution of the display glass. With the increasing use of glass in these electronic devices, it is becoming increasingly important to develop glass articles that maintain color clarity and clear display resolution.

Embodiments of the present disclosure are directed to glass articles having UV absorbers that minimize or eliminate UV photodarkening of glass articles. As used herein, "UV photodarkening" refers to the discoloration of a glass article upon exposure to UV light.

According to one embodiment, a glass article is provided. The glass article has a thickness of 1.3 mm, and, _SiO 2 of 54 to 75 mole%; of B 2 _{O 3} and _P 2 _{O 5;} 8 to 17 mole% _Al 2 _O 3 at least one, here, 0.1 _{mol% ≦ B 2 O 3 + P} 2 O 5 ≦ 19 mol%; 10 to 20 mol% of _R 2 O, wherein said _{R 2} O is _Na 2 O, At least one of K ₂ O and Li ₂ O is included; SnO _{2 of} more than 0 to 1 mol%; and an inorganic UV absorber are included. The inorganic UV absorber is 0.1 to 1.0 mol% of one or more kinds of metal ions or oxides thereof, and the metal ions are Ti, V, Mn, Fe, Cu, Ce, Ge, and Selected from the group consisting of combinations thereof; more than 0 to 500 ppm by mass of one or more metals or oxides thereof, wherein the metals are selected from the group consisting of Mo, Cr, Co and Ni. Or a combination thereof.

According to another embodiment, the glass article having a thickness of less than 1.3mm is from 0 to 12 mole% _B 2 _O 3; 0~7 mole% of _P 2 _{O 5;} and an inorganic UV absorber Including 3 mol%≦B ₂ O ₃ +P ₂ O ₅ ≦15 mol %.

According to yet another embodiment, there is provided a glass article that is substantially free of alkali metals and oxides. Alkali-free glass is 65 to 74 mol% of _SiO 2; 11 to 13 mol% of _Al 2 _O 3; _11~16 mol% of RO, wherein said RO is MgO, CaO, SrO, of BaO and ZnO 2 to 11 mol% of B ₂ O ₃ ; more than 0 to 1 mol% of SnO ₂ ; and an inorganic UV absorber, wherein the inorganic UV absorber is 0.1 to 1 0.0 mol% of one or more metal ions or oxides thereof, the metal ions being selected from the group consisting of Ti, V, Mn, Fe, Cu, Ce, Ge, and combinations thereof. >0 to 500 ppm by mass of one or more metals or oxides thereof, wherein the metals are selected from the group consisting of Mo, Cr, Co and Ni; or a combination thereof.

A further embodiment is directed to ZnO UV absorbers. For example, in one embodiment, the glass article is from 54 to 75 mol% of _SiO 2; 8 to 17 mol% of _Al 2 _O 3; _0.1~9 mol% of _B 2 _{O 3;} Optionally _P 2 O ₅ , where 0.1 mol%≦B ₂ O ₃ +P ₂ O ₅ ≦19 mol%; 10-20 mol% R ₂ O, where R ₂ O is Na ₂ O, K ₂ O, and one or more of Li ₂ O; 0 SnO ₂ to super to 1 mol%; and containing 0.5 to 10 mol% of ZnO.

In a further embodiment, the glass article is from 54 to 75 mol% of _SiO 2; 8 to 14 mol% of _Al 2 _O 3; _0~12 mol% of _B 2 _O 3; _0.1~7 mol% of _{P 2} O ₅ ; 10 to 20 mol% of R ₂ O, where R ₂ O includes one or more of Na ₂ O, K ₂ O, or Li ₂ O; 3 mol% ≦B ₂ O ₃ +P. ₂ O ₅ ≦15 mol%; and 0.5 to 10 mol% ZnO.

According to yet another embodiment, the glass article is free of alkali metals and oxides substantially, and, _SiO 2 of 65 to 74 mol%; 11 to 13 mol% of _Al 2 _O 3; 11 to 16 Mol% RO, wherein the RO is one or more of MgO, CaO, SrO, BaO and ZnO, and the glass article comprises 0.5-10 mol% ZnO; 2-11 2 _{O 3} mole% of _B; and, including SnO ₂ of greater than 0 up to 1 mol%.

The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the accompanying drawings.

The embodiments described in the drawings are illustrative in nature and are not intended to limit the invention defined in the claims. Furthermore, the individual features of the drawings will be more fully apparent and understood in view of the detailed description.

A graph showing the effect of TiO _{2 on} the absorbance/mm of the glass in Table 1 before and after exposure to UV. Graph showing the effect of TiO ₂ on the UV-induced absorbance of the glasses in Table 1. Another graph showing the effect of TiO ₂ on the UV-induced absorbance of the glasses in Table 1. A graph showing the effect of TiO ₂ on the UV-induced absorbance of the alkali-free display glasses of Table 3. Graph showing the effect of ZnO on the UV-induced absorbance of alkali aluminophosphosilicate glasses in Table 2 Graph showing the effect of ZnO on the UV-induced absorbance of the alkali aluminoborosilicate glasses of Table 4. Graph showing the effect of ZnO on the UV-induced absorbance of alkali-free glasses in Table 5 Graph showing the effect of SnO ₂ on the UV-induced absorbance of alkali-free glasses in Table 6

Embodiments of glass articles include UV absorbers suitable for reducing UV photodarkening. Many UV absorbers are designed to reduce UV photodarkening in glass articles, provided that these UV absorbers do not tend to photodarken to themselves. Without wishing to be bound by theory, lower levels of UV absorbers can significantly reduce or eliminate photodarkening in various glasses, whether or not the glasses are tempered. .. In certain embodiments, UV photodarkening reduction is achieved for aluminosilicate glasses. In one or more embodiments, the aluminosilicate glass can be an alkali aluminosilicate, non-alkali aluminosilicate, aluminoborosilicate, or aluminophosphosilicate glass.

In one embodiment, the inorganic UV absorber may include one or more metals or oxides of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ce, Ge, or combinations thereof. In certain embodiments, the inorganic UV absorber may comprise 0.1-1.0 mol% of one or more metal ions or oxides thereof, wherein the metal ions are Ti, V, Mn, Fe. , Cu, Ce, Ge, and combinations thereof. As an alternative to these UV absorbers, it may be desirable to include smaller amounts of other metallic UV absorbers inside the glass. For example, the inorganic UV absorber may include one or more metals or their oxides from greater than 0 (ie, greater than zero) up to 500 ppm by weight, the metals being Mo, Cr, Co and Ni. , Or a combination thereof. In yet another embodiment, the inorganic UV absorber may comprise up to 150 ppm by weight of one or more metals or oxides thereof, the metals being selected from the group consisting of Mo, Cr, Co and Ni. It

In an exemplary embodiment, the inorganic UV absorber is TiO ₂ . Various amounts of UV absorbers are contemplated herein. For example, a glass article may have 0.1 to 2 mol% inorganic UV absorber, or 0.1 to 1 mol% inorganic UV absorber, or 0.2 to 1 mol% inorganic UV absorber, or about 0. It may contain from 0.3 to 0.9 mol% of inorganic UV absorbers. In embodiments where a particular example, the glass article may comprise 0.2 to 1 mol% of TiO _2, or from about 0.3 to 0.9 mole% of TiO _2. Although most of the examples below show the effect of TiO ₂ , it is noted that the beneficial effect can also be achieved with other UV absorbers such as Sb ₂ O ₃ , CeO ₂ , Fe ₂ O ₃ . Shown in the drawings and described below.

An alternative approach is to dope the glass with zinc that is resistant to coloration induced when exposed to ultraviolet (UV) light or plasma cleaning processes. The addition of zinc can be applied to any glass composition to prevent coloration during exposure to deep UV or due to color center formation by plasma cleaning. Glass is, in one or more embodiments, 0.5-10 mol% ZnO, or 1-10 mol% ZnO, or 2-10 mol% ZnO, or even higher amounts are contemplated. It may contain 3-10 mol% ZnO, or 5-10 mol% ZnO.

Without wishing to be bound by theory, the use of ZnO instead of MgO is advantageous because it provides additional resistance to phase separation during heat treatment near the softening point.

Furthermore, without wishing to be bound by theory, glass articles demonstrating a reduction in UV photodarkening show that upon exposure to UV radiation, a UV absorbance of 2 or more/mm at a spectral wavelength of about 270 nm, and , Has an induced absorbance of less than 0.025 in the visible spectrum. As used herein, the visible spectrum includes wavelengths from 400 nanometers to 700 nanometers, and the ultraviolet (UV) spectrum includes wavelengths below the visible spectrum (ie, 400 nm or less), particularly wavelengths from 100 to 400 nm. including. In a further embodiment, the glass article can have a UV absorbance/mm of 2.2 or greater at a spectral wavelength of about 270 nm, or a UV absorbance/mm of 2.5 or greater at a spectral wavelength of about 270 nm. In a further embodiment, the glass can have an induced absorbance of 0.02 or less in the visible spectrum, or 0.01 or less in the visible spectrum.

As is well known to those skilled in the art, various UV irradiation wavelengths can cause UV photodarkening in glass articles unless a UV absorber is used. For example, without the use of UV absorbers, UV photodarkening can occur upon exposure to UV ozone radiation having a range of wavelengths, which is illuminated for 16 minutes at an irradiance of 28 mW cm ⁻¹ . sell.

Many glass thicknesses and compositions are planned. For example, the glass article may have a thickness of 1.3 mm or less, or 0.1 mm to 1.0 mm, or 0.2 mm to 0.8 mm. In an exemplary embodiment, the glass sheet has a thickness of less than 0.7 millimeters and the area of each major surface is greater than 60 square centimeters.

As mentioned above, the glass article is an aluminosilicate glass, such as an alkali aluminosilicate glass article. In one embodiment, the glass article comprises SiO ₂ and 8-17 mole% _Al 2 _{O 3} 54 to 75 mol%. In addition, the glass article comprises at least one of B ₂ O ₃ and P ₂ O ₅ , where 0.1 mol% ≦B ₂ O ₃ +P ₂ O ₅ ≦19 mol%. Furthermore, the glass article comprises a 12 to 20 mol% of _{R 2} O, wherein _{R 2} O _comprises Na 2 _{O, K} 2 O, and one or more of Li ₂ O.

Alternative component amounts are planned for aluminosilicate glass articles. For example, the glass article may comprise about 54 to 72 mol% of SiO _2, or from about 54 to 70 mole% of SiO _2, or about 54 to 65 mol% of SiO _2. Alternatively, the glass article may include about 63-75 mol% SiO ₂ . Further, silicate glass article aluminosilicate, 8 to 14% _Al 2 _{O 3,} or, alternatively, 11 to 17 mole% _Al 2 _{O 3,} or the like 11 to 13 mole% _Al 2 _{O 3,} Other planned ranges may be included. Furthermore, aluminosilicate glass article may include alkali amount in the range of 13 to 19 mol% of _R 2 O, or 14 to 18 mole% of _{R 2} O.

In the above embodiments, the aluminosilicate glass article may include 0.1 mol% ≤ B ₂ O ₃ +P ₂ O ₅ ≤ 19; however, for aluminoborosilicate or aluminoline silicate, the glass article is 1 mol% ≦B ₂ O ₃ +P ₂ O _{5 ≦} 15, or 3 mol% ≦B ₂ O ₃ +P ₂ O ₅ ≦15 mol%, or 2 mol% ≦B ₂ O ₃ +P ₂ O ₅ ≦10, or 3 mol%≦B ₂ O ₃ +P ₂ O ₅ ≦8 may be included. Include In certain embodiments, alumino phosphate silicates, up to 7 mol% of _P 2 _{O 5,} or 0.1 to 7 mol% of _P 2 _{O 5,} or 2 to 7 mol% of _P 2 _{O 5} to sell, aluminoborosilicate may include an 8 mole% maximum _B 2 _{O 3,} or 2-8 mol% of _B 2 _{O 3.} Furthermore, the glass article has a total Al ₂ O ₃ +B ₂ O ₃ +P ₂ O _{5 >} 12 mol %, or a total Al ₂ O ₃ +B ₂ O ₃ +P ₂ O ₅ >16 mol %, or Al ₂ O A sum of ₃ +B ₂ O ₃ +P ₂ O ₅ >19 mol% can be defined.

In another embodiment, the glass article may include an alkaline earth component. These alkaline earth components may be contained in a maximum amount of 17 mol% RO, which RO is one or more of MgO, CaO, SrO, BaO and ZnO. In a further embodiment, the glass article may comprise 0-7 mol% RO, or 0-4 mol% RO.

Furthermore, the composition of the glass article, _wherein: -3.5 <may be defined by the _{R 2 O + RO-Al 2} O 3 <10. In a further embodiment, the glass article has the _formula: -3.5 <may be defined by the _{R 2 O + RO-Al 2} O 3 <3.5.

In addition, the glass article comprises more than 0 and up to 1 mol% Sn or SnO ₂ , or 0.05 to 1 mol% Sn or SnO ₂ , or 0.1 to 1 mol% Sn or SnO ₂ , or 0. 0.1 to 0.5 mol% Sn or SnO ₂ may be included. In addition to Sn-based fining agents, it is planned to use other fining agents such as CeO ₂ . The use of environmentally friendly fining agents by glass manufacturers is increasing and the use of environmentally harmful fining agents such as As ₂ O ₃ and Sb ₂ O ₃ is decreasing. Thus, in one or more embodiments, the glass article may be substantially free of at least one of As ₂ O ₃ or Sb ₂ O ₃ . Additional embodiments may also be substantially free of other fining agents such as fluorine. In addition to its effectiveness as a fining agent, SnO ₂ is also effective in reducing photodarkening. For example, the inclusion of SnO ₂ results in an induced absorbance at 400 nm of about 0.02.

Improved resistance to UV photodarkening can also be achieved for alkali-free aluminosilicate glass articles. These alkali-free aluminosilicate glass composition, 65 to 72 mol% of _SiO 2, 11 to 13 mol% of _Al 2 _O 3; _11~16 mol% of RO, wherein said RO is MgO, CaO, One or more of SrO, BaO and ZnO; 2 to 11 mol% B ₂ O ₃ ; more than 0 to 1 mol% Sn or SnO ₂ ; and 0.1 to 1 mol% first. The inorganic UV absorbers mentioned may be included. In another embodiment, aluminosilicate glass article of alkali-free may include _P 2 _{O 5} 0-3 mol% of _P 2 _{O 5,} or 0-2 mol%.

As mentioned above, some of the glass articles of the present disclosure are toughened glass articles. Typically, glass articles, especially alkali aluminosilicate glass articles, can be chemically strengthened by ion exchange. In this process, the ions in the surface of the glass are replaced or exchanged with larger ions having the same valence or oxidation state. In embodiments where the glass article comprises, consists essentially of, or consists of, an alkali aluminosilicate glass, both the ions in the surface of the glass and the larger ions are, for example, Monovalent alkali metal cations such as Li ⁺ (when present in glass), Na ⁺ , K ⁺ , Rb ⁺ , and Cs ⁺ . Alternatively, the monovalent cations in the surface layer can be replaced with monovalent cations other than alkali metal cations such as Ag ⁺ .

The ion exchange process is typically performed by immersing the glass article in a molten salt bath containing larger ions that are exchanged for smaller ions in the glass. Including but not limited to bath composition and temperature, soaking time, number of times the glass is soaked in salt bath(s), use of multiple salt baths, additional steps such as annealing, cleaning, etc. It will be appreciated by those skilled in the art that the parameters of the ion exchange process are generally determined by the composition of the glass and the desired depth of the layers, and the compressive stress in the glass resulting from the tempering operation. By way of example, ion exchange of alkali metal-containing glasses can be accomplished by immersion in at least one molten bath, including but not limited to salts of larger alkali metal ions such as nitrates, sulfates, and chlorides. .. Immersion times range from about 15 minutes up to about 40 hours, while molten salt bath temperatures are typically in the range of about 380°C up to about 450°C. However, different temperatures and immersion times than those described above may also be used.

In addition, a non-limiting example of an ion exchange process in which the glass is immersed in multiple ion exchange baths with a cleaning and/or annealing step between the immersions is a salt bath in which the glass has different concentrations. Claiming priority of US Provisional Patent Application No. 61/079,995, filed Jul. 11, 2008, which is immersed in multiple sequential ion exchange treatments in "compressed surfaces for consumer applications. Under the name of the invention "Glass with Compressive Surface for Consumer Applications". Allan et al., U.S. patent application Ser. No. 12/500,650, filed Jul. 10, 2009; and the glass from the ion exchange in the first bath was diluted with effluent ions and then from the first bath. Also claims priority to US Provisional Patent Application No. 61/084,398, filed July 29, 2008, which is immersed in a second bath having a low concentration of effluent ions, "for scientific strengthening of glass. Under the title of the invention "Dual Stage Ion Exchange for Chemical Strengthening of Glass", Christopher M., published on November 20, 2012. See Lee et al., U.S. Pat. No. 8,312,739. The contents of US patent application Ser. No. 12/500,650 and US Pat. No. 8,312,739 are incorporated herein by reference in their entirety. Further, the glass compositions of the present disclosure can be drawn downward by processes known in the art such as slot draw, fusion draw, redraw, and the like, and have a liquidus viscosity of at least 13000 Pa·s (130 kilopoise). Have.

Experimental samples containing the compositions described in Tables 1-5 were cut into 1 mm thick discs of approximately 2.54 cm (1 inch) diameter and the surface was polished. Spectra of the samples were obtained by a spectrophotometer before and after 16 minutes of UV exposure (UVO cleaner model 7576, Jelight Co., Irvine, Calif., USA). The graphs of Figures 1-7 show the visible spectra after exposure to UV for various glasses.

As demonstrated in this figure and disclosure, glass samples were compared based on absorbance and induced absorbance measurements. Absorbance was calculated from the spectrum using Beer's law, where Absorbance=−log(transmittance). The induced absorbance in the sample is calculated by the computer as follows: Induced absorbance (A)=-log (permeability after test/permeability before test).

The absorbance against TiO ₂ content is plotted in Figures 1-3 for these samples.

Referring to Examples 1-9, the composition of TiO ₂ is increased from Example 1 to Example 9. Referring to FIG. 1, the addition of 0.1 TiO ₂ in Example 1 results in an absorbance/mm of approximately 1.0 to 1. at a UV wavelength of 270 nm as compared to Comparative Example 1 which does not contain TiO ₂ . It has increased to 5. Furthermore, the increase in TiO ₂ from Example 1 to Examples 2-9 increases the absorbance/mm from approximately 1.0 to at least 2.0 at the UV wavelength of 270 nm. Similar to that shown in Figures 2 and 3, the addition of TiO ₂ show a significant improvement in the induced absorbance. As shown in FIG. 3, the addition of TiO ₂ is greatly and thereby desirably reduces the induced absorbance. In particular, in Examples 2-9, the induced absorbance at 400 nm is closer to 0.0 compared to Comparative Example 1.

FIG. 4 shows a plot of the effect of TiO ₂ content for these samples.

Referring to examples 10 to 16 in Table 2, the increase in TiO _2, also decreases UV photodarkening in display glass alkali-free unreinforced. As shown, the composition of TiO ₂ increases from Example 10 to Example 16. Referring to FIG. 4, Comparative Example 2 containing no TiO ₂ only dropped to greater than 0.01 at 400 nm and less than 0.01 at longer visible wavelengths, whereas TiO 2 in Examples 10-16. _With the addition of ₂ , the UV-induced absorbance drops below 0.01 (1%) in the visible range of 400-450 nm.

FIG. 5 shows the effect of ZnO content in UV photodarkening for the samples in Table 3.

Referring to Examples 17 to 19 in Table 3 above, UV photodarkening is decreased due to an increase in ZnO. As shown in FIG. 5, in Comparative Example 3 containing no ZnO, the wavelength is more than 0.01 at 400 nm and longer than visible wavelength, that is, less than 0.01 at about 600 nm or more. With the addition of ZnO in Examples 17-19, the UV-induced absorbance drops below 0.01 (1%) in the visible range of 400-700 nm.

FIG. 6 shows the effect of ZnO content in UV photodarkening for the samples in Table 4.

Referring to Examples 20-26 in Table 4 above, increasing ZnO also reduces UV photodarkening in unreinforced, alkali-free display glass. As shown in FIG. 6, the induced absorbance of Comparative Example 4 without ZnO is greater than 0.01 at 400 nm and only drops to less than 0.01 at longer visible wavelengths. With the addition of ZnO at 20-26, the UV-induced absorbance drops below 0.01 (1%) in the visible range of 400-700 nm.

FIG. 7 shows the effect of ZnO and TiO ₂ in the alkali aluminosilicate glass of Table 5.

Referring to examples 27 to 35 in Table 5, the increase of ZnO and TiO _2, UV photodarkening from about 0.06 (6%) in the 400nm Comparative Example 5, 2.44 mol% of ZnO And Example 35 with 0.29 mol% TiO ₂ decreases synergistically to almost zero.

Without being bound by theory, Zn-containing phosphate glasses can be very stable when exposed to UV light as well as X-ray irradiation. Comparative Example 5 mainly contains MgO that is exchanged with ZnO. Exposure to UV ^photoreduces Fe ³⁺ to Fe ²⁺ by accepting electrons. MgO, in turn, can stabilize the resulting Fe ²⁺ and promote the formation of phosphorus-oxygen hole centers (POHC) in a detrimental way. Under UV exposure, these electrons may be excited to form electron color centers and/or hole centers. These color centers absorb light of a particular wavelength, especially in the visible range, thereby causing discoloration. POHC populations can also increase significantly after treatment with oxygen plasma treatment. Here, substitution of MgO with ZnO minimizes the MgO stabilization of this Fe ²⁺ , thereby substantially minimizing the number of electron color centers that lead to discoloration in the visible range.

FIG. 8 shows the effect of SnO ₂ in the alkali aluminosilicate glass of Table 6.

Referring to examples 36 to 44 in Table 6, the increase of SnO _2, for example, the alkali aluminosilicate glass (Examples 36 and 37), alkali aluminoborosilicate glass (Examples 38 and 39), and alkali UV photodarkening is synergistically reduced for all types of glass, including aluminosilicate glass (Examples 40-42), alkali-free display glass (Examples 43 and 44). Sample 37, which contains 0.2 mol% SnO ₂ has an induced absorbance of about 0.02 at 400 nm, compared to the example of an alkali aluminosilicate glass, while it contains 0 mol% SnO ₂ . Sample 36 has an induced absorbance at 400 nm of about 0.06. Similarly, sample 39 of an alkali aluminoborosilicate glass containing 0.2 mol% SnO ₂ has an induced absorbance at 400 nm of about 0.02, whereas alkali aluminoborosilicate glass containing 0 mol% SnO ₂ was used. Borosilicate glass sample 38 has an induced absorbance at 400 nm of about 0.12.

The most significant improvement is demonstrated for the alkali aluminosilicate glass samples. In particular, the alkali aluminosilicate glass sample 41 with 0.1 mol% SnO ₂ has an induced absorbance at 400 nm of about 0.04, while the sample 40 with 0 mol% SnO ₂ has It has an induced absorbance of about 0.16 at 400 nm. Moreover, the alkali aluminosilicate glass sample 42 with more SnO ₂ , ie 0.2 mol% SnO _2, has an induced absorbance of about 0.02 at 400 nm. Like the ion-exchanged alkali-containing glass (Example 36 - 42), SnO ₂ also photodarkening in display glass unreinforced non-alkali (Examples 43 and 44) also reduces. In particular, the display glass sample 44 containing 0.2 mol% SnO ₂ has an induced absorbance of about 0.01 at 400 nm, while the sample 43 containing 0 mol% SnO ₂ has about 400 nm. It has an induced absorbance of 0.04.

Furthermore, terms such as "preferably," "generally," "generally," and "typically" are used herein to limit the scope of the invention as claimed, or to a certain extent. It should be noted that the above features are not used for the purpose of including meanings which are significant, essential, or important to the structure or function of the claimed invention. Rather, these terms are merely intended to highlight alternative or additional features that may or may not be used in particular embodiments of the present disclosure.

It will be apparent that modifications and variations are possible without departing from the scope of the disclosure as defined by the appended claims. More particularly, some aspects of the present disclosure have been identified herein as preferred or particularly advantageous, but it is contemplated that the present disclosure need not necessarily be limited to these aspects. ..

The preferred embodiments of the present invention will be described below item by item.

Embodiment 1
In a glass article having a thickness of 1.3 mm or less,
54 to 75 mol% of _SiO 2;
8 to 17 mole% of _Al 2 _O 3;
At least one of B ₂ O ₃ and P ₂ O ₅ , where 0.1 mol% ≤ B ₂ O ₃ +P ₂ O ₅ ≤ 19 mol%;
10-20 mol% of _R 2 O, wherein said _{R 2} O comprises one or more of _Na 2 _{O, K} 2 O, and Li ₂ O;
A and inorganic UV absorbers,; 0 SnO ₂ to super to 1 mole%
0.1-1.0 mol% of one or more metal ions or oxides thereof, wherein the metal ions consist of Ti, V, Mn, Fe, Cu, Ce, Ge, and combinations thereof. Selected from metal ions or their oxides;
More than 0 to 500 ppm by mass of one or more metals or oxides thereof, the metals being selected from the group consisting of Mo, Cr, Co and Ni; or their oxides; or their A glass article comprising an inorganic UV absorber, including a combination.

Embodiment 2
It said glass article has the _{formula: -3.5 <R 2 O + RO} -Al 2 O 3 <10
2. The glass article according to embodiment 1, characterized by being defined by:

Embodiment 3
The glass article according to embodiment 1, wherein the glass article is a reinforced glass article.

Embodiment 4
In embodiment 1, wherein the glass article has a UV absorbance of 2 or more/mm at a spectral wavelength of about 270 nm and an induced absorbance of less than 0.025 for at least one wavelength of 400-700 nm. The glass article described.

Embodiment 5
The inorganic UV absorber contains 0.2 to 1.0 mol% of one or more kinds of metal ions or oxides thereof, and the metal ions are Ti, V, Mn, Fe, Cu, Ce, Ge, And the glass article according to Embodiment 1, which is selected from the group consisting of: and a combination thereof.

Embodiment 6
Said glass article, characterized in that it comprises a SnO ₂ of 0.05 to 1 mol%, the glass article according to the first embodiment.

Embodiment 7
The glass article according to embodiment 1, further comprising 0.1 to 17 mol% RO, wherein the RO is one or more of MgO, CaO, SrO, BaO and ZnO.

Embodiment 8
The glass article according to embodiment 1, wherein the thickness of the glass article is 0.1 to 1.0 mm.

Embodiment 9
Said glass article, 54-65 mol% of _SiO 2, 11 to 17 mol% of _Al 2 _O 3, 0 to 8 mol% _B 2 _O 3, 0 to 4 mol% RO, 0-7 mole% P ₂ O _5, comprises 13 to 19 mol% of _{R 2} O, _and, wherein the sum of the _{Al 2 O 3 + B 2 O} 3 + P 2 O 5> 19 is mol%, according to embodiment 1 Glass articles.

Embodiment 10
Embodiments characterized in that the inorganic UV absorber comprises 150 ppm or less by mass of one or more metals or oxides thereof, the metals being selected from the group consisting of Mo, Cr, Co and Ni. 1. The glass article according to 1.

Embodiment 11
Characterized in that said glass article, 0-12 mol% of _B 2 _O 3, 0 to 7 mol% of _P 2 _{O 5,} and containing 3 _{mol% ≦ B 2 O 3 + P} 2 O 5 ≦ 15 mol% The glass article according to Embodiment 1.

Embodiment 12
A glass article having a thickness of 1.3 mm or less, the glass article being substantially free of alkali metals and oxides, and
65 to 74 mol% of _SiO 2;
11-13 mol% Al ₂ O ₃ ;
11-16 mol% RO, where the RO is one or more of MgO, CaO, SrO, BaO and ZnO;
2 to 11 mol% of _B 2 _O 3;
In and inorganic UV absorbers,; 0 SnO ₂ to super to 1 mole%
0.1-1.0 mol% of one or more metal ions or oxides thereof, wherein the metal ions consist of Ti, V, Mn, Fe, Cu, Ce, Ge, and combinations thereof. Metal ions or their oxides selected from the group;
More than 0 to 500 ppm by mass of one or more metals or their oxides, wherein the metal is selected from the group consisting of Mo, Cr, Co and Ni; metal ions or their oxides; or A glass article comprising an inorganic UV absorber comprising a combination thereof.

Embodiment 13
Implementation, characterized in that the inorganic UV absorber comprises one or more metals or oxides thereof in an amount of 150 mass ppm or less, the metal being selected from the group consisting of Mo, Cr, Co and Ni. A glass article according to form 12.

Embodiment 14
The inorganic UV absorber contains 0.2 to 1.0 mol% of one or more kinds of metal ions or oxides thereof, and the metal ions are Ti, V, Mn, Fe, Cu, Ce, Ge, And a combination thereof, the glass article according to embodiment 12.

Embodiment 15
Said glass article, characterized in that it comprises a SnO ₂ of 0.1 to 1 mol%, the glass article of embodiment 12.

Embodiment 16
In embodiment 12, wherein the glass article has a UV absorbance of 2 or more/mm at a spectral wavelength of about 270 nm and an induced absorbance of less than 0.025 for at least one wavelength of 400-700 nm. The glass article described.

Embodiment 17
The glass article according to embodiment 12, wherein the thickness of the glass article is 0.1 to 1.0 mm.

Embodiment 18.
It said glass article is characterized in that it comprises a _P 2 _{O 5} 0-3 mol%, the glass article of embodiment 12.

Embodiment 19.
In a glass article having a thickness of 1.3 mm or less,
54 to 75 mol% of _SiO 2;
8 to 17 mole% of _Al 2 _O 3;
0.1 to 9 mol% of _B 2 _O 3;
Optionally P ₂ O ₅ , where 0.1 mol% ≦B ₂ O 3 +P ₂ O ₅ ≦19 mol%;
10-20 mol% of _R 2 O, wherein said _{R 2} O comprises one or more of _Na 2 _{O, K} 2 O, and Li ₂ O;
0 SnO up super to 1 mole% _2; and 0.5 to 10 mol% of ZnO
Including glass articles.

Embodiment 20
Said glass article, characterized in that it comprises SiO ₂ and 8 to 14 mole% _Al 2 _{O 3} 63 to 75 mol%, the glass article of embodiment 19.

Embodiment 21
Said glass article has the _formula: -3.5 <characterized in that it is defined by _{R 2 O + RO-Al 2} O 3 <10, the glass article of embodiment 19.

Embodiment 22
Glass article according to embodiment 19, characterized in that said glass article comprises 1 to 10 mol% ZnO.

Embodiment 23
20. A glass article according to embodiment 19, characterized in that the glass article is a reinforced glass article.

Embodiment 24
Glass article according to embodiment 19, characterized in that the glass article has an induced absorbance of less than 0.01 for at least one wavelength between 400 and 700 nm.

Embodiment 25
It said glass article is characterized in that it comprises a SnO ₂ of 0.05 to 1 mol%, the glass article of embodiment 19.

Embodiment 26
20. Embodiment 19 characterized in that the glass article comprises 0.5 to 17 mol% RO, which RO is one or more of MgO, CaO, SrO, ZnO, and BaO. Glass articles.

Embodiment 27
Glass article according to embodiment 19, characterized in that the thickness of the glass article is 0.1-1.0.

Embodiment 28
Said glass article, 54-65 mol% of _SiO 2, 11 to 17 mol% of _Al 2 _O 3, 0.1 to 8 mole% of _B 2 _O 3, 0 to 4 mol% of RO, 0 to 7 mol % P ₂ O ₅ , 13-19 mol% R ₂ O, and the total of Al ₂ O ₃ +B ₂ O ₃ +P ₂ O ₅ >19 mol%. Glass articles.

Embodiment 29
In a glass article having a thickness of 1.3 mm or less,
54 to 75 mol% of _SiO 2;
Of 8 to 14 mol% _Al 2 _O 3;
0-12 mol% of _B 2 _O 3;
0.1-7 mol% P ₂ O ₅ ;
10-20 mol% R ₂ O, wherein the R ₂ O comprises one or more of Na ₂ O, K ₂ O, or Li ₂ O;
3 mol%≦B ₂ O ₃ +P ₂ O ₅ ≦15 mol%; and 0.5-10 mol% ZnO
Including glass articles.

Embodiment 30
It said glass article is characterized in that it comprises a SiO ₂ of 63 to 75 mol%, the glass article of embodiment 29.

Embodiment 31
30. The glass article of embodiment 29, wherein the glass article comprises 1-10 mol% ZnO.

Embodiment 32
Said glass article has the _formula: -3.5 <characterized in that it is defined by _{R 2 O + RO-Al 2} O 3 <10, the glass article of embodiment 29.

Embodiment 33
30. The glass article according to embodiment 29, wherein the glass article is a reinforced glass article.

Embodiment 34
Glass article according to embodiment 29, characterized in that the glass article has an induced absorbance of less than 0.01 for at least one wavelength between 400 and 700 nm.

Embodiment 35
It said glass article is characterized in that it comprises a SnO ₂ of 0.05 to 1 mol%, the glass article of embodiment 29.

Embodiment 36
Embodiment 29, wherein the glass article comprises 0.5 to 17 mol% RO, wherein the RO is one or more of MgO, CaO, SrO, ZnO, and BaO. Glass articles.

Embodiment 37
30. The glass article according to embodiment 29, wherein the thickness of the glass article is 0.1-1.0 mm.

Embodiment 38
Said glass article, 54-65 mol% of _SiO 2, 11 to 17 mol% of _Al 2 _O 3, 0 to 8 mol% of _B 2 _O 3, 0 to 4 mol% of RO, 0.1 to 7 moles % of _P 2 _O 5, characterized in that it contains 13 to 19 mol% of _R 2 O, and the sum of the _{Al 2 O 3 + B 2 O} 3 + P 2 O 5> 19 mol%, of embodiment 29 Glass articles.

Embodiment 39
A glass article having a thickness of 1.3 mm or less, the glass article being substantially free of alkali metals and oxides, and
65 to 74 mol% of _SiO 2;
11-13 mol% Al ₂ O ₃ ;
11-16 mol% RO, wherein the RO is one or more of MgO, CaO, SrO, BaO and ZnO, and the glass article comprises 0.5-10 mol% ZnO;
2 to 11 mol% of _B 2 _{O 3;} and 0 SnO ₂ to super to 1 mole%
Including glass articles.

Embodiment 40
40. The glass article of embodiment 39, wherein the glass article comprises 1-10 mol% ZnO.

Embodiment 41
40. The glass article according to embodiment 39, wherein the glass article has an induced absorbance of less than 0.01 for at least one wavelength of 400-700 nm.

Embodiment 42
It said glass article is characterized in that it comprises a 0.1 to 1 mole percent of Sn or SnO _2, glass article of embodiment 39.

Embodiment 43
The glass article according to embodiment 39, wherein the thickness of the glass article is 0.1-1.0 mm.

Embodiment 44
It said glass article is characterized in that it comprises a _P 2 _{O 5} 0-3 mol%, the glass article of embodiment 39.

Claims (8)

In a glass article having a thickness of 1.3 mm or less,
54 to 75 mol% of _SiO 2;
8 to 17 mole% of _Al 2 _O 3;
At least one of B ₂ O ₃ and P ₂ O ₅ , where 0.1 mol% ≤ B ₂ O ₃ +P ₂ O ₅ ≤ 19 mol%;
10-20 mol% of _R 2 O, wherein said _{R 2} O comprises one or more of _Na 2 _{O, K} 2 O, and Li ₂ O;
0 _SnO up super to 1 mole% 2;
0.5-10 mol% ZnO; and
0 . 1 to 1.0 mol% of one or more metal ions or oxides thereof, wherein the metal ions are selected from the group consisting of Ti, V, Mn, Fe, Cu, Ce, Ge, and combinations thereof. is the metal ion or including no machine UV absorbers and their oxides;
Including glass articles. It said glass article has the _formula: -3.5 <characterized in that it is defined by _{R 2 O + RO-Al 2} O 3 <10, the glass article according to claim 1. Said glass article, 54-65 mol% of _SiO 2, 11 to 17 mol% of _Al 2 _O 3, 0 to 8 mol% _B 2 _O 3, 0 to 4 mol% RO, 0-7 mole% P ₂ O _5, 13 to 19 mol% of _R 2 O, _and, characterized in that it comprises a total of> 19 mol% of _{Al 2 O 3 + B 2 O} 3 + P 2 O 5, according to claim 1 or 2 Glass articles. Characterized in that said glass article, 0-12 mol% of _B 2 _O 3, 0 to 7 mol% of _P 2 _{O 5,} and containing 3 _{mol% ≦ B 2 O 3 + P} 2 O 5 ≦ 15 mol% The glass article according to any one of claims 1 to 3. The inorganic UV absorber contains 0.2 to 1.0 mol% of one or more kinds of metal ions or oxides thereof, and the metal ions are Ti, V, Mn, Fe, Cu, Ce, Ge, and characterized in that it is selected from the group consisting of glass article according to any one of claims 1-4. Said glass article, characterized in that it comprises a 0.1 to 1 mole percent of Sn or SnO _2, glass article according to any one of claims 1-5. Said glass article, and having two or more UV absorbance / mm, and the induced less than 0.025 for at least one wavelength of 400~700nm absorbance in the spectral wavelength of 270 nm, according to claim 1 to 6 The glass article according to any one of 1. Characterized in that the thickness of the glass article is 0.1 to 1.0 mm, the glass article according to any one of claims 1-7.

Images